EP0915929B1 - Masterbatches containing vulcanising agents - Google Patents

Masterbatches containing vulcanising agents Download PDF

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Publication number
EP0915929B1
EP0915929B1 EP97935652A EP97935652A EP0915929B1 EP 0915929 B1 EP0915929 B1 EP 0915929B1 EP 97935652 A EP97935652 A EP 97935652A EP 97935652 A EP97935652 A EP 97935652A EP 0915929 B1 EP0915929 B1 EP 0915929B1
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Prior art keywords
copolymer
masterbatches
ethylene
acrylate
les
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German (de)
French (fr)
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EP0915929A1 (en
Inventor
Dominique Bonhomme
Walter Pfrengle
Nour Eddine El Bounia
Jean-Michel Pierrot
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Arkema France SA
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Atofina SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers

Definitions

  • the present invention relates to masterbatches containing vulcanizing agents and more particularly to thermoplastic masterbatches supported by copolymers of ethylene and at least one unsaturated carboxylic acid ester. They are useful, for example, for introducing vulcanizing agents into elastomers. It also relates to a process for the preparation of masterbatches containing vulcanizing agents and supported by thermoplastic copolymers of ethylene.
  • Vulcanized elastomers result from the mixture of an elastomer such as, for example, a styrene-butadiene copolymer with fillers, plasticizers, antioxidants, a vulcanizing agent, one or more accelerators, optionally an activator, then this mixture is shaped. and heated to cause vulcanization which is a crosslinking reaction.
  • an elastomer such as, for example, a styrene-butadiene copolymer with fillers, plasticizers, antioxidants, a vulcanizing agent, one or more accelerators, optionally an activator
  • the vulcanizing agents, accelerator, activator, antioxidants are used at relatively low doses when compared to the other ingredients (fillers, plasticizers). As their role is fundamental in the crosslinking reaction, it is necessary that their distribution in the mixture to be vulcanized is optimal. For this, it is advantageous to introduce these products into the mixture in the form of masterbatches.
  • these masterbatches use as an support an elastomer such as an EPDM (ethylene-propylene-diene copolymer), an EPR (ethylene-propylene copolymer), an SBR (copolymer-styrene-butadiene), or an NBR (copolymer nitrile-butadiene).
  • an elastomer such as an EPDM (ethylene-propylene-diene copolymer), an EPR (ethylene-propylene copolymer), an SBR (copolymer-styrene-butadiene), or an NBR (copolymer nitrile-butadiene).
  • these masterbatches are very loaded with additives. It is necessary to choose as a support a polymer which can be easily dispersed in the mixture to be vulcanized.
  • this support it is therefore advantageous for this support to have an affinity with the mixtures to be vulcanized.
  • the present invention relates to thermoplastic masterbatches having at least one copolymer (A) of ethylene and at least one ester of unsaturated carboxylic acid and comprising vulcanizing agents.
  • Masterbatches could contain only part of the vulcanization system such as sulfur and the accelerator would be added separately to the elastomer.
  • the masterbatches also contained the other usual additives of the elastomers to be vulcanized, such as plasticizers, carbon black, silica, carbonate, talc, flame retardants. These additives often represent quantities of the same order of magnitude or greater than the elastomer itself, and are always in much greater quantities than the vulcanization system. Such a masterbatch would make no sense. However, the masterbatches of the invention may contain a little plasticizer as will be explained later.
  • the elastomers to be vulcanized can be for example natural rubber, polyisoprene, SBR, NBR, EPDM, polychloroprene, butyl rubber or polyethers such as epychlorohydrin rubbers.
  • the esters can come from the reaction of an unsaturated carboxylic acid with a monoalcohol having from 1 to 24 carbon atoms.
  • a monoalcohol having from 1 to 24 carbon atoms By way of example, mention may be made of (meth) acrylates alkyl of which the alkyl has from 1 to 24 carbon atoms. Examples of acrylate or methacrylates are methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate.
  • These esters can be introduced into A by grafting (on polyethylenes) or by direct copolymerization.
  • the amount of additives can be from 50 to 90% by weight of the masterbatch.
  • this amount is 80 to 90%.
  • the density of the masterbatches can thus be between 1.1 and 5.5.
  • the copolymer (A) is such that the masterbatch is solid and non-sticky at ambient temperature and plastic at the processing temperatures, that is to say during mixing with the polymer and the other additives that 'is added to the polymer in addition to the masterbatch.
  • This temperature can vary with the nature of the polymer and the additives; as a general rule, the elastomer and all of its additives, including the masterbatch of the invention, cannot be mixed above 100 or 110 ° C. without risking the onset of vulcanization.
  • the masterbatches of the invention are plastic, advantageously at temperatures above 80 or 90 ° C. They can thus be dispersed in the polymers while remaining in an area where there is for example no risk of pre-vulcanization.
  • the MOONEY ML 1 + 4 viscosity at 50 ° C of the masterbatches is between 15 and 25.
  • the masterbatch can comprise a plasticizer such as for example a parafinic or naphthenic oil to facilitate the incorporation of the additives and / or to adjust the viscosity.
  • a plasticizer such as for example a parafinic or naphthenic oil to facilitate the incorporation of the additives and / or to adjust the viscosity.
  • a copolymer (A) having at least either the temperature of melting either the glass transition temperature or the VICAT point above room temperature and below the mixing temperature with the polymer in which the masterbatch is added.
  • a copolymer (A) is chosen having a melting temperature of approximately 50 to 120 ° C. its VICAT point can be less than 50 ° C.
  • a mixture of copolymers (A) can be used even if none, one or more does not meet the above conditions, provided that the masterbatch has the characteristics mentioned above.
  • (A) is an ethylene- (meth) acrylate copolymer containing up to 50% by weight of (meth) acrylate and preferably 20 to 40%.
  • These polymers can be random copolymers produced by high pressure radical catalysis, that is to say between 500 and 3000 bars.
  • (A) can be an ethylene- (meth) acrylate-maleic anhydride copolymer or an ethylene - (meth) acrylate-glycidyl methacrylate copolymer.
  • It can comprise up to 50% by weight of (meth) acrylate and up to 10% by weight of glycidyl anhydride or methacrylate.
  • the polymer (B) is chosen so that the masterbatches of the invention have the properties mentioned above.
  • the masterbatches of the invention comprise a copolymer (A) ethylene / (meth) alkyl acrylate and a copolymer (B) ethylene / (meth) alkyl acrylate / maleic anhydride.
  • the copolymer (B) can comprise up to 50% by weight of alkyl (meth) acrylate and up to 10% by weight of maleic anhydride.
  • the proportions of (A) and (B) can be such that (by weight) l 5 ⁇ AT B ⁇ 10 1 and advantageously 60 to 80 parts of (A) for 20 to 40 parts of (B).
  • the masterbatches of the invention can be produced both by techniques in the rubber industry and those in the thermoplastics industry. It is thus possible to use extruders, mixers, twin screws, possibly homogenize on cylinders.
  • the masterbatches of the invention can be easily filtered, it is filtration for example at 500, 200 or 140 ⁇ m according to the specifications. This is an important advantage of the invention, due to the thermoplastic behavior and the absence of anti-sticking product.
  • the masterbatches of the invention are prepared on machines used for thermoplastics, in particular single or twin-screw extruders. We can thus further reduce or even remove the talc and possibly add waxes which remove any stickiness.
  • the residence time in the extruders is much shorter than in the kneaders or the cylinders of devices in the rubber industry; so we can work a little warmer this which allows the use of copolymers (A) with a higher melting point, for example around 110 ⁇ 120 ° C.
  • EVA-based masterbatches can also contain antioxidants and various additives like those mentioned above.
  • the invention is a process for preparing masterbatches containing vulcanizing agents and having as support either at least one copolymer (A) of ethylene and at least one ester of unsaturated carboxylic acid or at least one copolymer ethylene and a vinyl ester of saturated carboxylic acid, said process consisting in mixing the support and the vulcanizing agents in an extruder.
  • the process of the invention also relates to the preparation of masterbatches based on the copolymer (A) which has been described above.
  • the process of the invention also relates to the supports of masterbatches based on a copolymer of ethylene and of a vinyl ester of saturated carboxylic acid (for example EVA) in admixture with other thermoplastic polymers for example those mentioned in the polymers (B) mentioned above and which are different from the ethylene-vinyl ester copolymer of saturated carboxylic acid and different from the copolymer (A).
  • a copolymer of ethylene and of a vinyl ester of saturated carboxylic acid for example EVA
  • other thermoplastic polymers for example those mentioned in the polymers (B) mentioned above and which are different from the ethylene-vinyl ester copolymer of saturated carboxylic acid and different from the copolymer (A).
  • the mixtures were prepared in an internal mixer and then on follower cylinders.
  • Masterbatches are prepared at 90% by weight of zinc oxide (Zno).
  • Formula 1 according to the invention: LOTRYL 2 4.4% OIL 4.6% STEARINE 1% ZNO 90%
  • Formula 2 according to the invention LOTRYL 5 4.4% OIL 4.6% STEARINE 1% ZNO 90%

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)

Abstract

The invention relates to thermoplastic master batches having at least one copolymer (A) of ethylene and of at least one unsaturated carboxylic acid ester as support and comprising vulcanization agents for rubbers. The invention also relates to a process for the preparation of master batches containing vulcanization agents and having a thermoplastic ethylene copolymer as support, this process consisting in using an extruder.

Description

La présente invention concerne des mélanges maîtres contenant des agents de vulcanisation et plus particulièrement des mélanges maîtres thermoplastiques ayant pour support des copolymères de l'éthylène et d'au moins un ester d'acide carboxylique insaturé. Ils sont utiles par exemple pour introduire des agents de vulcanisation dans des élastomères. Elle concerne aussi un procédé de préparation de mélanges maîtres contenant des agents de vulcanisation et ayant pour support des copolymères thermoplastiques de l'éthylène.The present invention relates to masterbatches containing vulcanizing agents and more particularly to thermoplastic masterbatches supported by copolymers of ethylene and at least one unsaturated carboxylic acid ester. They are useful, for example, for introducing vulcanizing agents into elastomers. It also relates to a process for the preparation of masterbatches containing vulcanizing agents and supported by thermoplastic copolymers of ethylene.

Les élastomères vulcanisés résultent du mélange d'un élastomère tel que par exemple un copolymère styrène-butadiène avec des charges, des plastifiants, des antioxydants, un agent de vulcanisation, un ou plusieurs accélérateurs, éventuellement un activateur, puis ce mélange est mis en forme et chauffé pour provoquer la vulcanisation qui est une réaction de réticulation.Vulcanized elastomers result from the mixture of an elastomer such as, for example, a styrene-butadiene copolymer with fillers, plasticizers, antioxidants, a vulcanizing agent, one or more accelerators, optionally an activator, then this mixture is shaped. and heated to cause vulcanization which is a crosslinking reaction.

Les agents de vulcanisation, accélérateur, activateur, antioxydants, sont utilisés à des doses relativement faibles si on les compare aux autres ingrédients (charges, plastifiants). Comme leur rôle est fondamental dans la réaction de réticulation, il est nécessaire que leur répartition dans le mélange à vulcaniser soit optimale. Pour cela, il est avantageux d'introduire ces produits dans le mélange sous forme de mélange maitres.The vulcanizing agents, accelerator, activator, antioxidants, are used at relatively low doses when compared to the other ingredients (fillers, plasticizers). As their role is fundamental in the crosslinking reaction, it is necessary that their distribution in the mixture to be vulcanized is optimal. For this, it is advantageous to introduce these products into the mixture in the form of masterbatches.

En règle générale, ces mélanges maitres utilisent comme support un élastomère tel qu'un EPDM (copolymère éthylène-propylène-diène), un EPR (copolymère éthylène-propylène), un SBR (copolymère-styrène-butadiène), ou un NBR (copolymère nitrile-butadiène).In general, these masterbatches use as an support an elastomer such as an EPDM (ethylene-propylene-diene copolymer), an EPR (ethylene-propylene copolymer), an SBR (copolymer-styrene-butadiene), or an NBR (copolymer nitrile-butadiene).

Par définition, ces mélanges maîtres sont très chargés en additifs. Il est nécessaire de choisir comme support un polymère qui puisse se disperser facilement dans le mélange à vulcaniser.By definition, these masterbatches are very loaded with additives. It is necessary to choose as a support a polymer which can be easily dispersed in the mixture to be vulcanized.

Il est donc avantageux que ce support ait une affinité avec les mélanges à vulcaniser.It is therefore advantageous for this support to have an affinity with the mixtures to be vulcanized.

Ces mélanges maitres se présentent en général sous forme de bandes ou de granulés. L'une des difficultés rencontrées dans leur utilisation réside dans leur tendance à s'agglomérer au cours du stockage. Ce phénomène est dû au collant manifesté par le support aux températures habituelles de stockage. Cette agglomération empêche souvent l'utilisation du produit dans les installations usuelles de transport et pesées automatiques qui équipent les ateliers de mélange.These masterbatches are generally in the form of strips or granules. One of the difficulties encountered in their use lies in their tendency to agglomerate during storage. This phenomenon is due to the stickiness manifested by the support at the usual storage temperatures. This agglomeration often prevents the use of the product in the usual transport and automatic weighing facilities that equip the mixing workshops.

Selon l'art antérieur on remédie à cet inconvénient par addition d'agent anti collant, par exemple le talc, ajouté par pulvérisation au moment de la granulation ou de la confection des bandes de mélange maître. Ce procédé a pour inconvénient d'introduire un produit supplémentaire qu'il est toujours difficile de repandre de façon régulière.According to the prior art, this drawback is remedied by the addition of an anti-sticking agent, for example talc, added by spraying at the time of granulation or the preparation of the masterbatch strips. This process has the disadvantage of introducing an additional product which it is always difficult to spread regularly.

La demanderesse a maintenant trouvé que des mélanges maîtres ayant pour support des copolymères de l'éthylène et d'esters d'acides carboxyliques insaturés avaient de nombreux avantages :The Applicants have now found that masterbatches supported by copolymers of ethylene and of esters of unsaturated carboxylic acids have numerous advantages:

Ces polymères de l'éthylène grâce à leur polarité se dispersent facilement dans la plupart des polymères ; ils ont un point VICAT faible qui facilite la dispersion du mélange maître, enfin à la température ambiante le mélange maître est solide et non collant ce qui empêche toute agglomération au stockage quelle que soit la présentation sous forme de bande ou de granulé et ceci avec éventuellement l'addition de faibles quantités d'agent antiadhérent tel que par exemple le talc. En utilisant les mélanges maîtres de la présente invention pour vulcaniser des élastomères on n'observe pas de dégradation des propriétés des caoutchoucs vulcanisés par rapport aux caoutchoucs vulcanisés avec les mélanges maîtres de l'art antérieur.These polymers of ethylene, thanks to their polarity, are easily dispersed in most polymers; they have a weak VICAT point which facilitates the dispersion of the masterbatch, finally at room temperature the masterbatch is solid and non-sticky which prevents any agglomeration during storage whatever the presentation in the form of a strip or of granules and this with possibly the addition of small amounts of antiadhesive agent such as for example talc. By using the masterbatches of the present invention to vulcanize elastomers, no degradation of the properties of the vulcanized rubbers is observed with respect to the rubbers vulcanized with the masterbatches of the prior art.

La présente invention concerne des mélanges maîtres thermoplastiques ayant pour support au moins un copolymère (A) de l'éthylène et d'au moins un ester d'acide carboxylique insaturé et comprenant des agents de vulcanisation.The present invention relates to thermoplastic masterbatches having at least one copolymer (A) of ethylene and at least one ester of unsaturated carboxylic acid and comprising vulcanizing agents.

A titre d'exemple, on peut citer :

  • les systèmes de vulcanisation au soufre constitués de soufre associé aux accélérateurs de vulcanisation tels que les sels métalliques de dithiocarbamates (diméthyl dithiocarbamate de zinc, de tellure...), les mono di et tetrasulfures de thiurame (tetramethyl disulfure de thiurame...), les sulferamides, les dérivés de la morpholine, les guanidines.
By way of example, we can cite:
  • sulfur vulcanization systems made up of sulfur associated with vulcanization accelerators such as the metallic salts of dithiocarbamates (zinc dimethyl dithiocarbamate, tellurium ...), thiuram mono di and tetrasulfides (thiuram tetramethyl disulfide ...) , sulferamides, morpholine derivatives, guanidines.

Ces systèmes peuvent aussi contenir de l'oxyde de zinc associé éventuellement à de l'acide stéarique qui sont des activateurs de vulcanisation des élastomères dieniques,

  • les systèmes de vulcanisation donneurs de soufre dans lesquels la majorité du soufre utilisé pour la réticulartion provient de molécules soufrées telles que les polysulfures de thiurames, le disulfure de mercaptobenzothiazole etc...,
  • les systèmes de vulcanisation à base d'oxydes métalliques, particulièrement pour des élastomères halogénés (polychloroprène par exemple). Il s'agit notamment de l'oxyde de zinc,
  • les systèmes de vulcanisation aux résines phénoliques constitués de résines formophénoliques difonctionnelles pouvant être halogénées et associées à des chlorures métalliques ou l'oxyde de zinc,
  • les systèmes de vulcanisation aux peroxydes, dans lesquels tous les donneurs de radicaux libres peuvent être utilisés, par exemple le peroxyde de dicumyle, en association avec l'oxyde de zinc et l'acide stéarique,
  • les vulcanisants à base de diamines (orthotoluidyl guanidine, diphénylguanidine...) ou de diamines bloquées telles que le carbamate d'hexaméthylène diamine,
  • les systèmes d'accélération à base de dérivés de la thiourée comme l'éthylthiourée ou la diethylthiourée.
These systems can also contain zinc oxide possibly associated with stearic acid which are activators of vulcanization of dienic elastomers,
  • sulfur donor vulcanization systems in which the majority of the sulfur used for crosslinking originates from sulfur molecules such as thiuram polysulfides, mercaptobenzothiazole disulfide, etc.,
  • vulcanization systems based on metal oxides, particularly for halogenated elastomers (polychloroprene for example). These include zinc oxide,
  • vulcanization systems with phenolic resins consisting of difunctional formophenolic resins which can be halogenated and associated with metal chlorides or zinc oxide,
  • peroxide vulcanization systems, in which all the free radical donors can be used, for example dicumyl peroxide, in combination with zinc oxide and stearic acid,
  • vulcanizing agents based on diamines (orthotoluidyl guanidine, diphenylguanidine, etc.) or blocked diamines such as hexamethylene diamine carbamate,
  • acceleration systems based on thiourea derivatives such as ethylthiourea or diethylthiourea.

Les mélanges maîtres de l'invention peuvent en plus contenir un ou plusieurs des produits suivants :

  • des anti oxydants,
  • des anti ozonants,
  • des absorbeurs d'ultraviolets,
  • des agents gonflants,
  • du noir de carbone.
The masterbatches of the invention can additionally contain one or more of the following products:
  • antioxidants,
  • anti ozonants,
  • UV absorbers,
  • blowing agents,
  • carbon black.

Les mélanges maîtres pourraient ne contenir qu'une partie du système de vulcanisation tel que le soufre et on ajouterait l'accélérateur séparément dans l'élastomère.Masterbatches could contain only part of the vulcanization system such as sulfur and the accelerator would be added separately to the elastomer.

On ne sortirait pas du cadre de l'invention si les mélanges maîtres contenaient aussi les autres additifs habituels des élastomères à vulcaniser tels que les plastifiants, le noir de carbone, la silice, le carbonate, le talc, les ignifugeants. Ces additifs représentent souvent des quantités du même ordre de grandeur ou plus importantes que l'élastomère, lui-même et sont toujours en quantités beaucoup plus importantes que le système de vulcanisation. Un tel mélange maître n'aurait aucun sens. Cependant, les mélanges maîtres de l'invention peuvent contenir un peu de plastifiant ainsi qu'il sera expliqué plus loin.It would not go beyond the scope of the invention if the masterbatches also contained the other usual additives of the elastomers to be vulcanized, such as plasticizers, carbon black, silica, carbonate, talc, flame retardants. These additives often represent quantities of the same order of magnitude or greater than the elastomer itself, and are always in much greater quantities than the vulcanization system. Such a masterbatch would make no sense. However, the masterbatches of the invention may contain a little plasticizer as will be explained later.

Les élastomères à vulcaniser peuvent être par exemple le caoutchouc naturel, le polyisoprène, le SBR, le NBR, l'EPDM, le polychloroprène, le caoutchouc butyle ou les polyéthers tels que les caoutchoucs épychlorhydrine.The elastomers to be vulcanized can be for example natural rubber, polyisoprene, SBR, NBR, EPDM, polychloroprene, butyl rubber or polyethers such as epychlorohydrin rubbers.

S'agissant du copolymère (A), les esters peuvent provenir de la réaction d'un acide carboxylique insaturé avec un monoalcool ayant de 1 à 24 atomes de carbone. A titre d'exemple, on peut citer les (méth)acrylates d'alkyle dont l'alkyle a de 1 à 24 atomes de carbone. Des exemples d'acrylate ou de méthacrylates sont le méthacrylate de méthyle, l'acrylate d'éthyle, l'acrytate de n-butyle, l'acrylate d'isobutyle et l'acrylate de 2-éthylhexyle. Ces esters peuvent être introduites dans A par greffage (sur des polyéthylènes) ou par copolymérisation directe.As regards the copolymer (A), the esters can come from the reaction of an unsaturated carboxylic acid with a monoalcohol having from 1 to 24 carbon atoms. By way of example, mention may be made of (meth) acrylates alkyl of which the alkyl has from 1 to 24 carbon atoms. Examples of acrylate or methacrylates are methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate. These esters can be introduced into A by grafting (on polyethylenes) or by direct copolymerization.

La quantité d'additifs (c'est-à-dire d'agents de vulcanisation et d'autres produits éventuels) peut être de 50 à 90 % en poids du mélange maître. Avantageusement cette quantité est de 80 à 90 %. La densité des mélanges maîtres peut être ainsi entre 1,1 et 5,5.The amount of additives (that is to say vulcanizing agents and other possible products) can be from 50 to 90% by weight of the masterbatch. Advantageously, this amount is 80 to 90%. The density of the masterbatches can thus be between 1.1 and 5.5.

Avantageusement, le copolymère (A) est tel que le mélange maître est solide et non collant à la température ambiante et plastique aux températures de mise en oeuvre, c'est-à-dire au cours du mélange avec le polymère et les autres additifs qu'on ajoute dans le polymère en plus du mélange maître. Cette température peut varier avec la nature du polymère et des additifs ; on ne peut pas en règle générale effectuer le mélange de l'élastomère et de tous ses additifs, y compris le mélange maître de l'invention, au-dessus de 100 ou 110° C sans risquer de provoquer un début de vulcanisation.Advantageously, the copolymer (A) is such that the masterbatch is solid and non-sticky at ambient temperature and plastic at the processing temperatures, that is to say during mixing with the polymer and the other additives that 'is added to the polymer in addition to the masterbatch. This temperature can vary with the nature of the polymer and the additives; as a general rule, the elastomer and all of its additives, including the masterbatch of the invention, cannot be mixed above 100 or 110 ° C. without risking the onset of vulcanization.

Les mélanges maîtres de l'invention sont plastiques, avantageusement à des températures supérieures à 80 ou 90°C. On peut ainsi les disperser dans les polymères tout en restant dans un domaine ou il n'y a pas par exemple de risque de prévulcanisation.The masterbatches of the invention are plastic, advantageously at temperatures above 80 or 90 ° C. They can thus be dispersed in the polymers while remaining in an area where there is for example no risk of pre-vulcanization.

A titre d'exemple, la viscosité MOONEY ML 1 + 4 à 50° C des mélanges maîtres est comprise entre 15 et 25.For example, the MOONEY ML 1 + 4 viscosity at 50 ° C of the masterbatches is between 15 and 25.

Le mélange maître peut comprendre un plastifiant tel que par exemple une huile parafinique ou naphténique pour faciliter l'incorporation des additifs et/ou ajuster la viscosité.The masterbatch can comprise a plasticizer such as for example a parafinic or naphthenic oil to facilitate the incorporation of the additives and / or to adjust the viscosity.

La demanderesse a trouvé que pour que le mélange maître respecte les conditions ci-dessus, à savoir solide à la température ambiante et plastique aux températures de mise en oeuvre, il était avantageux de choisir un copolymère (A) ayant au moins soit la température de fusion soit la température de transition vitreuse, soit le point VICAT au dessus de la température ambiante et en dessous de la température de mélange avec le polymère dans lequel on ajoute le mélange maître. De préférence on choisit un copolymère (A) ayant une température de fusion d'environ 50 à 120° C son point VICAT peut être inférieur à 50° C.The Applicant has found that in order for the masterbatch to comply with the above conditions, namely solid at room temperature and plastic at processing temperatures, it was advantageous to choose a copolymer (A) having at least either the temperature of melting either the glass transition temperature or the VICAT point above room temperature and below the mixing temperature with the polymer in which the masterbatch is added. Preferably, a copolymer (A) is chosen having a melting temperature of approximately 50 to 120 ° C. its VICAT point can be less than 50 ° C.

On peut utiliser un mélange de copolymères (A) même si aucun, un ou plusieurs ne respecte pas les conditions ci-dessus pourvu que le mélange maître possède les caractéristiques citées plus haut.A mixture of copolymers (A) can be used even if none, one or more does not meet the above conditions, provided that the masterbatch has the characteristics mentioned above.

De préférence, (A) est un copolymère éthylène-(méth)acrylate d'alkyle contenant jusqu'à 50 % en poids de (méth)acrylate et de préférence 20 à 40 %. Ces polymères peuvent être des copolymères statistiques produits par catalyse radicalaire à haute pression, c'est-à-dire entre 500 et 3 000 bars.Preferably, (A) is an ethylene- (meth) acrylate copolymer containing up to 50% by weight of (meth) acrylate and preferably 20 to 40%. These polymers can be random copolymers produced by high pressure radical catalysis, that is to say between 500 and 3000 bars.

Selon une autre forme de l'invention, le copolymère (A) peut comprendre d'autres monomères (M1) greffés ou polymérisés, à titre d'exemple de ces monomères, on peut citer :

  • les acides carboxyliques insaturés par exemple ceux ayant de 2 à 20 atomes de carbone tels que les acides acrylique, méthacrylique, maléique, fumarique et itaconique ;
  • les dérivés fonctionnels des acides précédents par exemple les anhydrides, les dérivés amides, les dérivés imides et les sels métalliques tels que les sels de métaux alcalins ;
  • les epoxydes insaturés tels que par exemple le (méth)acrylate de glycidyle, l'allylglycidyléther, le vinylglycidyléther, le maléate de glycidyle, l'itaconate de glycidyle, le 2-cyclohexène-1-glycidyléther, le cyclohéxène-4,5-diglycidylcarboxylate, le cyclohéxène-4-glycidyl carboxylate, le 5-norbornène-2-méthyl-2-glycidyl carboxylate et l'endocis-bicyclo (2,2,1)-5-heptène-2,3-diglycidyl dicarboxylate.
According to another form of the invention, the copolymer (A) can comprise other grafted or polymerized monomers (M1), by way of example of these monomers, mention may be made of:
  • unsaturated carboxylic acids, for example those having 2 to 20 carbon atoms such as acrylic, methacrylic, maleic, fumaric and itaconic acids;
  • functional derivatives of the above acids, for example anhydrides, amide derivatives, imide derivatives and metal salts such as alkali metal salts;
  • unsaturated epoxides such as, for example, glycidyl (meth) acrylate, allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate, glycidyl itaconate, 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidylcarboxylate , cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endocis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate.

Par exemple (A) peut être un copolymère éthylène-(méth)acrylate d'alkyle-anhydride maléique ou un copolymère éthylène -(méth)acrylate d'alkyle-méthacrylate de glycidyle.For example (A) can be an ethylene- (meth) acrylate-maleic anhydride copolymer or an ethylene - (meth) acrylate-glycidyl methacrylate copolymer.

Il peut comprendre jusqu'à 50 % en poids de (meth)acrylate et jusqu'à 10 % en poids d'anhydride ou de methacrylate de glycidyle.It can comprise up to 50% by weight of (meth) acrylate and up to 10% by weight of glycidyl anhydride or methacrylate.

Selon une autre forme de l'invention, le mélange maître peut comprendre un autre polymère (B) différent de (A) choisi parmi :

  • les copolymères éthylène -ester d'acide carboxylique insaturé greffé ou copolymérisé avec un ou plusieurs des monomères (M1) cités plus haut à condition que ces copolymères soient différents de (A) ;
  • les copolymères éthylène/esters vinyliques d'acides carboxyliques saturés pouvant être greffés ou copolymérisés avec au moins un monomère choisi parmi (M1) et les esters d'acides carboxyliques insaturés ;
  • les polyoléfines homo ou copolymères pouvant être greffées avec un monomère choisi parmi (M1) et les esters d'acides carboxyliques insaturés ;
  • les élastomères EPR (éthylène-propylène) ;
  • les élastomères cités plus haut dans lesquels on ajoute les mélanges maîtres de l'invention ;
  • les élastomère précédents greffés par (M1) et avantageusement l'anhydride maléique,
  • les copolymères blocs styrène-butadiène-styrène (SBS), styrène-éthylène/butène-styrène (SEBS) et styrène-isoprène-styrène (SIS) éventuellement greffés.
According to another form of the invention, the masterbatch can comprise another polymer (B) different from (A) chosen from:
  • ethylene-ester unsaturated carboxylic acid copolymers grafted or copolymerized with one or more of the monomers (M1) mentioned above, provided that these copolymers are different from (A);
  • ethylene / vinyl ester copolymers of saturated carboxylic acids which can be grafted or copolymerized with at least one monomer chosen from (M1) and esters of unsaturated carboxylic acids;
  • homo or copolymer polyolefins which can be grafted with a monomer chosen from (M1) and esters of unsaturated carboxylic acids;
  • EPR (ethylene-propylene) elastomers;
  • the elastomers mentioned above in which the masterbatches of the invention are added;
  • the preceding elastomers grafted with (M1) and advantageously maleic anhydride,
  • styrene-butadiene-styrene (SBS), styrene-ethylene / butene-styrene (SEBS) and styrene-isoprene-styrene (SIS) block copolymers optionally grafted.

Le polymère (B) est choisi de telle sorte que les mélanges maîtres de l'invention aient les propriétés citées plus haut.The polymer (B) is chosen so that the masterbatches of the invention have the properties mentioned above.

Avantageusement, les mélanges maîtres de l'invention comprennent un copolymère (A) éthyiène/(méth)acrylate d'alkyle et un copolymère (B) éthylène/(méth)acrylate d'alkyle/anhydride maléique.Advantageously, the masterbatches of the invention comprise a copolymer (A) ethylene / (meth) alkyl acrylate and a copolymer (B) ethylene / (meth) alkyl acrylate / maleic anhydride.

Le copolymère (B) peut comprendre jusqu'à 50 % en poids de (meth)acrylate d'alkyle et jusqu'à 10 % en poids d'anhydride maléique.The copolymer (B) can comprise up to 50% by weight of alkyl (meth) acrylate and up to 10% by weight of maleic anhydride.

Les proportions de (A) et (B) peuvent être telles que (en poids) l 5 ≤ A B ≤ 10 1    et avantageusement 60 à 80 parties de (A) pour 20 à 40 parties de (B). Les mélanges maîtres de l'invention peuvent être fabriqués aussi bien par les techniques de l'industrie des caoutchoucs que celles de l'industrie des thermoplastiques. On peut ainsi utiliser les extrudeuses, les mélangeurs, les bivis, eventuellement homogénéiser sur cylindres. Les mélanges maîtres de l'invention peuvent être facilement filtrés, il s'agit de filtration par exemple à 500, 200 ou 140 µm selon les spécifications. C'est un avantage important de l'invention, dû au comportement thermoplastique et à l'absence de produit anti collant.The proportions of (A) and (B) can be such that (by weight) l 5 ≤ AT B ≤ 10 1 and advantageously 60 to 80 parts of (A) for 20 to 40 parts of (B). The masterbatches of the invention can be produced both by techniques in the rubber industry and those in the thermoplastics industry. It is thus possible to use extruders, mixers, twin screws, possibly homogenize on cylinders. The masterbatches of the invention can be easily filtered, it is filtration for example at 500, 200 or 140 μm according to the specifications. This is an important advantage of the invention, due to the thermoplastic behavior and the absence of anti-sticking product.

Avantageusement les mélanges maîtres de l'invention sont préparés sur des machines utilisées pour les thermoplastiques en particulier les extrudeuses mono ou bi-vis. On peut ainsi encore réduire ou même supprimer le talc et éventuellement ajouter des cires qui suppriment tout caractère collant. De plus le temps de séjour dans les extrudeuses est beaucoup plus faible que dans les malaxeurs ou les cylindres des appareils de l'industrie du caoutchouc ; on peut donc travailler un peu plus chaud ce qui permet d'utiliser des copolymères (A) à point de fusion plus élevé par exemple vers 110 ~ 120°C.Advantageously, the masterbatches of the invention are prepared on machines used for thermoplastics, in particular single or twin-screw extruders. We can thus further reduce or even remove the talc and possibly add waxes which remove any stickiness. In addition, the residence time in the extruders is much shorter than in the kneaders or the cylinders of devices in the rubber industry; so we can work a little warmer this which allows the use of copolymers (A) with a higher melting point, for example around 110 ~ 120 ° C.

L'art antérieur FR 2139409 a décrit des mélanges maîtres contenant des agents de vulcanisation et ayant pour support des copolymères éthylène-acétate de vinyle (EVA). Ces mélanges maîtres sont fabriqués sur des cylindres et des granulateurs de l'industrie du caoutchouc. La demanderesse a découvert que ces mélanges maîtres pouvaient être fabriqués sur des machines utilisées pour les thermoplastiques telles que par exemple les extrudeuses mono ou bi-vis. Les avantages principaux sont :

  • le caractère collant est de moindre importance pendant la fabrication
  • on peut travailler un peu plus chaud (le temps de séjour est plus faible).
The prior art FR 2139409 has described masterbatches containing vulcanizing agents and supported by ethylene-vinyl acetate (EVA) copolymers. These masterbatches are produced on cylinders and granulators in the rubber industry. The Applicant has discovered that these masterbatches could be manufactured on machines used for thermoplastics such as, for example, single or twin screw extruders. The main advantages are:
  • stickiness is of less importance during manufacture
  • you can work a little warmer (the residence time is shorter).

Ces mélanges maîtres à base d'EVA peuvent aussi contenir des anti oxydants et divers additifs comme ceux cités plus haut.These EVA-based masterbatches can also contain antioxidants and various additives like those mentioned above.

Ainsi l'invention est un procédé de préparation de mélanges maîtres contenant des agents de vulcanisation et ayant pour support soit au moins un copolymère (A) de l'éthylène et d'au moins un ester d'acide carboxylique insaturé soit au moins un copolymère de l'éthylène et d'un ester vinylique d'acide carboxylique saturé ledit procédé consistant à mélanger le support et les agents de vulcanisation dans une extrudeuse.Thus, the invention is a process for preparing masterbatches containing vulcanizing agents and having as support either at least one copolymer (A) of ethylene and at least one ester of unsaturated carboxylic acid or at least one copolymer ethylene and a vinyl ester of saturated carboxylic acid, said process consisting in mixing the support and the vulcanizing agents in an extruder.

Le procédé de l'invention concerne aussi la préparation des mélanges maîtres à base du copolymère (A) qu'on a décrit plus haut.The process of the invention also relates to the preparation of masterbatches based on the copolymer (A) which has been described above.

Le procédé de l'invention concerne aussi les supports de mélanges maîtres à base de copolymère d'éthylène et d'ester vinylique d'acide carboxylique saturé (par exemple l'EVA) en mélange avec d'autres polymères thermoplastiques par exemple ceux cités dans les polymères (B) cités plus haut et qui sont différents du copolymère éthylène-ester vinylique d'acide carboxylique saturé et différents du copolymère (A).The process of the invention also relates to the supports of masterbatches based on a copolymer of ethylene and of a vinyl ester of saturated carboxylic acid (for example EVA) in admixture with other thermoplastic polymers for example those mentioned in the polymers (B) mentioned above and which are different from the ethylene-vinyl ester copolymer of saturated carboxylic acid and different from the copolymer (A).

ExemplesExamples

Dans les exemples, on désigne par :

LOTRYL 1:
un copolymère éthylène-acrylate de n-butyle de proportion en poids 65 / 35 de MFi.900 (190° C - 2,16 kg).
LOTRYL 2:
un copolymère éthylène/acrylate de méthyle de proportion en poids 71/29 de MFi. 2 - 3,5.(190° C - 2,16 kg), le point de fusion est 61°C et VICAT <40°C.
LOTADER 1:
un copolymère éthylène-acrylate d'éthyle-anhydride maléique de proportions en poids 91/6/3 et MFi.200 (190° C -2,16kg), le point de fusion est 100°C et le VICAT 57°C.
LOTRYL 3:
un copolymère éthylène-acrylate de butyle de proportion en poids 65/35 de MFI 40 (190°C - 2,16 kg) le point de fusion est 67°C et le VICAT <40°C.
LOTRYL 4:
un copolymère éthylène-acrylate de méthyle de proportion en poids 65/35 de MFI 4, 5 / 6 le point de fusion est 50°C et le VICAT <40°C.
LOTRYL 5:
un copolymère éthylène-acrylate de butyle de proportion en poids 65/35 de MFI 260/350 le point de fusion est 66°C et le VICAT <40°C.
MBTS:
désigne le disulfure de mercapto benzothiazole
DPTU:
désigne le diphénylthiourée
HUILE :
désigne une huile de paraffine.
In the examples, we denote by:
LOTRYL 1:
an ethylene-n-butyl acrylate copolymer with a weight proportion of 65/35 of MFi.900 (190 ° C. - 2.16 kg).
LOTRYL 2:
an ethylene / methyl acrylate copolymer of weight proportion 71/29 from MFi. 2 - 3.5. (190 ° C - 2.16 kg), the melting point is 61 ° C and VICAT <40 ° C.
LOTADER 1:
an ethylene-ethyl acrylate-maleic anhydride copolymer of proportions by weight 91/6/3 and MFi.200 (190 ° C -2.16 kg), the melting point is 100 ° C and VICAT 57 ° C.
LOTRYL 3:
an ethylene-butyl acrylate copolymer with a weight proportion of 65/35 of MFI 40 (190 ° C - 2.16 kg) the melting point is 67 ° C and the VICAT <40 ° C.
LOTRYL 4:
an ethylene-methyl acrylate copolymer with a 65/35 proportion by weight of MFI 4, 5/6 the melting point is 50 ° C. and the VICAT <40 ° C.
LOTRYL 5:
an ethylene-butyl acrylate copolymer of proportion by weight 65/35 of MFI 260/350 the melting point is 66 ° C. and the VICAT <40 ° C.
MBTS:
denotes mercapto benzothiazole disulfide
DPTU:
denotes diphenylthiourea
OIL :
denotes a paraffin oil.

Les mélanges ont été préparés dans un mélangeur interne puis sur des cylindres suiveurs.The mixtures were prepared in an internal mixer and then on follower cylinders.

Les résultats sont reportés sur les tableaux 1 à 3 suivants. Les pourcentages sont en poids. Tableau 1 Composition en parties 1 2 3 4 5 6 MBTS 75 75 80 75 75 75 Huile 10 10 10 12 10,5 11 Lotryl 1 1.75 5.25 1,75 Lotryl 2 5.25 3,25 5 6 5 Lotader 1 1.75 Talc 5 5 5 5,5 6 Stearine 3 3 3 3 3 3 Comportement sur le mélangeur interne bon bon bon bon bon bon Comportement sur les cylindres suiveurs bon bon bon bon bon bon Filtration bonne bonne bonne bonne bonne bonne Viscosité MOONEY ML1 +4 (50°C) 16,6-18,8 15,2-15,1 19,8-21,5 24,5-23,5 19,5-19,6 18,7-17-8 The results are reported in the following tables 1 to 3. The percentages are by weight. Table 1 Composition in parts 1 2 3 4 5 6 MBTS 75 75 80 75 75 75 Oil 10 10 10 12 10.5 11 Lotryl 1 1.75 5.25 1.75 Lotryl 2 5.25 3.25 5 6 5 Lotader 1 1.75 Talc 5 5 5 5.5 6 Stearine 3 3 3 3 3 3 Behavior on the internal mixer Well Well Well Well Well Well Behavior on follower cylinders Well Well Well Well Well Well Filtration good good good good good good MOONEY ML1 +4 viscosity (50 ° C) 16.6-18.8 15.2-15.1 19.8-21.5 24.5-23.5 19.5-19.6 18.7-17-8

On prépare des mélanges maîtres à 90 % en poids d'oxyde de zinc (Zno).
    Formule 1 selon l'invention : LOTRYL 2 4.4 % HUILE 4.6 % STEARINE 1 % ZNO 90 %     Formule 2 selon l'invention LOTRYL 5 4.4 % HUILE 4.6 % STEARINE 1 % ZNO 90 % Masterbatches are prepared at 90% by weight of zinc oxide (Zno).
Formula 1 according to the invention: LOTRYL 2 4.4% OIL 4.6% STEARINE 1% ZNO 90% Formula 2 according to the invention LOTRYL 5 4.4% OIL 4.6% STEARINE 1% ZNO 90%

On compare leur viscosité Mooney avec celle de formulations de l'art antérieur à base d'EPM ou de SBR.Their Mooney viscosity is compared with that of formulations of the prior art based on EPM or SBR.

Les résultats sont sur le tableau 3 ci-après : Tableau 3 50°C 80°C 100°C FORMULE 1 64 14 8 90 % ZNO FORMULE 2 23 10 7 90 % ZNO FORMULE 3 base EPM 78 39 26 85 % ZNO FORMULE 4 base SBR 94 50 30 85 % ZNO The results are in Table 3 below: Table 3 50 ° C 80 ° C 100 ° C FORMULA 1 64 14 8 90% ZNO FORM 2 23 10 7 90% ZNO FORMULA 3 EPM base 78 39 26 85% ZNO FORMULA 4 base SBR 94 50 30 85% ZNO

Claims (5)

  1. Thermoplastic masterbatches containing at least one copolymer (A) of ethylene and of at least one unsaturated carboxylic acid ester as support and comprising curing agents chosen from:
    - sulphur-containing curing systems
    - sulphur-donating curing systems
    - curing systems based on metal oxides
    - accelerator systems based on thiourea derivatives
    and in which the copolymer (A) has a melting point of between 50°C and 120°C.
  2. Masterbatches according to Claim 1, also comprising one or more products chosen from antioxidants, anti-ozonizers, ultraviolet stabilizers swelling agents and carbon black.
  3. Masterbatches according to either of the preceding claims, in which the amount of curing agents and of other optional products is from 50 to 90% by weight of the masterbatch.
  4. Masterbatches according to any one of the preceding claims, in which the copolymer (A) is an ethylene/alkyl (meth)acrylate copolymer.
  5. Masterbatches according to any one of the preceding claims, also comprising a polymer (B) chosen from ethylene/alkyl (meth)acrylate/maleic anhydride copolymers.
EP97935652A 1996-07-29 1997-07-29 Masterbatches containing vulcanising agents Expired - Lifetime EP0915929B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9609502 1996-07-29
FR9609502 1996-07-29
PCT/FR1997/001418 WO1998004617A1 (en) 1996-07-29 1997-07-29 Masterbatches containing vulcanising agents

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KR20020089894A (en) * 2001-05-25 2002-11-30 한국타이어 주식회사 Masterbatch for tire rubber composition
US7402619B2 (en) * 2005-03-31 2008-07-22 Kraton Polymers U.S. Llc Cross-linking compositions for polymer-modified asphalt compositions
FR2910005B1 (en) * 2006-12-15 2009-08-21 Mlpc Internat Sa MIXTURES WITH A COPOLYMER OF ETHYLENE AND ALPHA-OLEFIN CONTAINING VULCANIZATION AGENTS
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GB1389342A (en) * 1971-05-11 1975-04-03 Rhein Chemie Rheinau Gmbh Process for the production of rubber mixtures
SE8303538L (en) * 1983-06-20 1984-12-21 Unifos Kemi Ab COMPOSITIONS CONTAINING LINES POLYETTE AND COPOLYMERS OF ONE AND ACRYLATE
JPH0781011B2 (en) * 1987-01-28 1995-08-30 富士写真フイルム株式会社 Resin composition for coloring master batch used for packaging material for photographic light-sensitive material
US4857600A (en) * 1988-05-23 1989-08-15 Union Carbide Corporation Process for grafting diacid anhydrides
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KR20000029531A (en) 2000-05-25
BR9711608A (en) 1999-08-24
CA2261627C (en) 2005-02-08
ATE205867T1 (en) 2001-10-15
AU3855597A (en) 1998-02-20
CN1113924C (en) 2003-07-09
ES2164363T3 (en) 2002-02-16
WO1998004617A1 (en) 1998-02-05
KR100443295B1 (en) 2004-08-09
DE69706866T2 (en) 2002-04-11
CN1226907A (en) 1999-08-25
JP2000515918A (en) 2000-11-28

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